Detergent composition



1 In. "it f 1 f 3,083,166 Patented Mar. 26, 1963 "ice this invention. Moreover, the tensile strength can often 3,083,166 be increased beyond that of the same fabric merely treated with water along. i gi h spartanburgns'c" asslgho' to Textile fabrics which can be treated with the compog agz sg g g ggz spartanburg 5 sitions of this invention include those comprising the No gawing Filed Man 9, 1960, No' 13,727 natural proteinaceous fibers, e.g., wool, the natural cellu- 5 Claims (Cl. 252 142) losrc fibers, e.g., cotton and linen, the modified cellulosrc fibers, e.g., viscose rayon, the cellulose acetates and ethers, This invention relates to novel textile treating comand the man-made fibers, e.g., polymeric hexamethylene positions and to methods for their use. adipamides, e.g., the nylons, polyacrylonitriles including According to this invention, one or more of the ad those sold under the trademark Orion, polymeric vinylvantages described hereinafter are obtained by treating idene chlorides and polyester fibers, e.g., polymeric ethyla textile fabric with an aqueous solution of a composiene glycol terephthalic acid esters, including those sold tion comprising a water soluble sulfonic acid condensaunder the trademark Dacron, mixtures of the above tion product of aldeh des and aro and mixtures with other fibers. The preferred fabrics or the water soluble salts thereof, and a water soluble are those consisting entirely of or containing a substanacidic material having a molecular weight of less than tial amount, e.g., 40% or more, of wool or cotton. Par- 300, in an amount sufiicient to render the resulting aqueticularly outstanding results are obtained with pure wool ous solution initially acidic at a pH of less than about 5 and pure cotton fabrics. The fibers used in the textile but less than the amount which would injure the fabric. fabrics, especially cotton and wool, can be treated in It is an object of this invention to provide a composithe form of an unwoven mass or as threads or yarns tion which enhances the cleansing power of detergents. and the treatment of these fibers in this form as well as It is another object to provide a composition which in the knitted or woven form is within the scope of this enhances the brightening and whitening properties of invention. textile fluorescent brightening agents. All of the compositions and the process of this inven- 5 Still another object is to provide certain novel additive tion comprise using (1) a water soluble sulfonic acid compositions for detergents. condensation product of an aldehyde and an aromatic A further object is to provide certain novel detergent sulfonic a a Water Soluble Salt thereof, compositions. an acidic material having a molecular weight of less than I A further object is to provide a method of treating 300.

textile fibers to give at least one of a cleaner product, Included in the compounds falling within the definiimproved brightness and whiteness, improved hand, tion of (l), i.e., diarylalkane disulfonic acids and their warmth, greater tear strength, a higher flex abra ion salts, and preferred are the condensation products of an resistance, and improved tensile strength. aldehyde and a carbocyclic aryl sulfonic acid, e.g., those Other objects will be apparent to those skilled in the having the general formula R-OsS-aryl-(CHz) -aryl-SOa-R well known m the art F f hathral wherein R is hydrogen, the ammonium (NH radical, them i commonly used texhlo fabnos yellow or or a metal, preferably an alkali metal, e.g., sodium or otherwise discolor on exposure to sun and/or arr. Many 0 Potassium, is a connecting carbocyclic aryl radi detergents presently on the market seek to overcome this ca], phenyl, tolyl, xylyl hydroxyphenyl, cresyl died y mcorporahhg a fluorescent brightening agent fonyloxyphenyl, and n is an integer from 1-10, pre fera- 1 or optical bleach 111 the detergent composition. These My The aryl group can in addition to the sulfonyl F E "3 often very expensive- T compositions of oxy group, contain one or more substituents, e.g., amino, thls mvehhoh enhance the hnghtohmg Powof offhahy hydroxy, nitro, halo e.g., chloro, and sulfonyloxy. Inof these agents and often permit a reduction 1n the cluded within this preferred class of compounds are the dio f o those oxpehslvo agohts h' the who phenylmethane disulfonic acids, dinaphthylmethane disulmarntamrng the same degree of brightening prop rt e fonic acids, ditolymethane disulfonic acids, dixylylmethane It has also been found that theeleaflsmgproremqs of disulfonic acids, di-hydroxyphenyl-methane disulfonic ootorgohhs can be o by moorporatmg thoreln a acids, dicresylmethane disulfonic acids, di-chloronaphthyloomhoslhoh oh thls lhvohhoh, While at the Same hme methane disulfonic acids, di-nitronaphthyl-methane dip ng eddlhonal advantages to the resultant detergent sulfonic acids, diphenylmethane-meta-tetrasulfonic acids composition. and di-hydroxynaphthyl-methane disulfonic acids. This In h f h one of the tests of the q y of class of compounds are well known in the art and are a fabno 15 Its n handle- The more expensive described inmore detail with further examples in Grasser fibers: are charaeterlled by a eoft, P g hand as and Enna, Synthetic Tannins, paragraphs 35 to 68 emPhfied y the more eXPenSIVe grades of cottons and (1922), Technical Press Ltd. They are prepared by the h cashmere Wools- Unfortunately, Washing textile well known reaction of an arylsulfonic acid with an al- 1163 h detergents SOePS Seldom retains the hand dehyde, preferably formaldehyde, to produce a hydrocar- Present ln'the oflglnnl Product and more Often Pmdnees bon bridge between two of the arylsulfonic acid molea pmgresslyely Poorer hand- A detergent incorporating cules. It is possible, by employing a mixture of startthe composition of this invention can reverse this trend ing arylsulfonic acids, to produce a mixed sulfonic acid toward a poorer hand and often can produce a better condensation product, i.e., one aryl group differs from hand than was P in the fabric as Originally P the other connected aryl group. However, ordinarily p the disulfonic acid products are symmetrical. There are It rs also known in the art that detergent washing of many of these disulfonic acid condensation products availa fabric composed of natural fibers often reduces at least able commercially. one of the tensile and tear strength and flex abrasion The acidic materials having a molecular weight of resistance of the fabric. It has been found that this less than 300 which are employed in the compositions of deleterious effect of washing of textile fabrics, especially this invention are limited to those compounds which are wool and cotton fabrics, with a detergent can be reduced capable of lowering an aqueous solution thereof, in the by incorporating in the detergent the composition of presence of the selected condensation product, to a pH of less than about 5, and preferably in an amount which will produce a pH higher than 2. This can readily be ascertained by testing various concentrations of the acidic material alone in an aqueous solution. As the other ingredient and/or ingredients of the claimed composition are preferably neutral or acidic, it will be apparent that the amount of a selected acidic material necessary to achieve the desired pH in the compositions of this invention will be about the same as, or slightly less, than the amount which alone will produce the desired pH. Similarly, the effect of the acidic material on a selected fabric at a particular concentration can be determined by tests well known in the textile art, e.g., tensile, tear and/or flex abrasion. These acidic materials preferably have a dissociation constant (pKa) of between about 5 10- and about 1X10 and more desirably between about 1x10" and about 1x10-.

The preferred acidic materials are, either organic or inorganic acids, i.e., as distinguished from acidic salts such 'as, for example, sodium acid sulfate. Examples of inorganic acids are sulfuric, phosphoric, and hydrochloric. It will be apparent to those skilled in the art that these acids, in high concentration, can injure many fabrics. For this reason, the organic acids are preferred and, in fact, ordinarily give superior results than are obtained with the inorganic acids, even when the latter is used in an amount which does not injure the fabric.

Examples of the organic acids which can be used in the process of this invention include acetic, formic, chloroacetic, dichloroacetic, benzenesulfonic, hydroxyacetic, p-toluenesulfonic, citric lactic, tartaric, gluconic, and oxalic acid. Preferred are the carboxylic and especially the polyhydroxycarboxylic acids. wit! gives UlLaQdjDgllll1Sln d.iS. OIdlnaI l pre prred.

If'fi? composition is intended for textile mill use,'then the stronger, e.g., inorganic acids can be used, particularly if the fabric to be treated is wool. However, for home use, the organic acids and particularly the polyhydroxycarboxylic acids, especially citric acid, are preferred.

The amount of the above compounds which should be applied to the selected fabric acn be varied over a fairly wide range. For example, good results can be obtained employing the condensation product in the range of about 0.01 to about 5%, calculated on the weight of the dry fabric being treated. Lesser amounts tend to diminish some of the advantages that are obtained by this ingredient whereas greater amounts tend to render the process commercially or economically unfeasible. Generally, between about 0.25 and 2.0% give the optimum desired results. Similarly, the amountof acid which can be employed can be varied considerably, e.g., from about 0.001 to 30%, and preferably between about 0.25 and 20%, and more desirably about 0.25 and calculated on the weight of the dry fabric. However, the amount used should be such that a 0.5% aqueous. solution of the resulting composition will have an initial pH of between about 2 gI 1 d a.hou-L5. The amount and nature of the acidic material should be such that the resulting composition will not injure the fabric to be treated at normal concentrations. It is preferred to operate at or below the isoelectric point of the wool, which is ordinarily around 4.5, but can range from about 3.7 to 5.2. The exact amount of each ingredient which should be employed will depend on the fabric being treated and, to a certain extent, on the results desired, with the usual proportion of condensation product to acidic material being from 1:100 to 6:1. For example, improved hand, improved tensile and tearstrength, warmth, improved flex abrasion resistance, and elasticity will not always occur simultaneously and varying the amount of condensation product and acidic material will enhance each of these properties to a varying degree.

The compositions of this invention are preferaby employed as additives for detergents, especially the anionic,

e.g., the alkylbenzene-sulfonic acid, and the nonionic, e.g., alkaryl polyglycol, detergents. Among the former are the compounds of the formula alkyl-phenyl-SO M wherein alkyl is the alkyl radical of a fatty acid, and M is hydrogen or an alkali metal, which compounds comprise a well known class of anionic detergents and include sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium oleylbenzenesulfonate and sodium cetylbenzenesul- :fonate. Others are the alkali metal salts of the higher .alkylsulfonic acids and the alkali metal dialkyl sulfosuccinates, e.g., sodium dioctylsulfosuccinate, and sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, sodium oleyl-p-anisidinesulfonate, sodium tetradecanesulfonate, sodium diisopropylnaphthalenesulfonate, sodium 0ctylphenoxyethoxyethylsulfonate, etc., and the alkali metal alkyl sulfates, e.g., sodium lauryl sulfate. Ordinarily, the alkali metal salts, rather than the free acid detergents are preferred.

As nonionic detergents there can be employed alkylphenolethylene oxides, e.g., p-isooctyl phenol-polyethylene oxide (10 ethylene oxide units), long chain alcohol-ethylene oxide condensation products, e.g., dodecyl alcoholpolyethylene oxides having 4 to 16 ethylene oxide units per molecule, polyglycerol monolaurate, glycol dioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquiole- :ate, the condensation products of ethylene oxide with sorbitan esters of long chain fatty acids (Tweens), etc.

The preferred detergent to be employed with the compositions of this invention are the alkali metal salts of the alkylbenzenesulfonates, especially sodium dodecylbenzenesulfonate.

As stated hereinbefore, the compositions of this invention enhance the whitening and brightening characteristics of detergent additives known as textile fluorescent brightening agents. Thus, the detergent compositions of this invention preferably comprise these agents, employed in the amounts normally used in detergents or in somewhat lesser amounts, because of the enhanced properties of these agents.

As the fluorescent brightening agent there can be employed any of the conventional ones, such as those mentioned in Colour Index, Society of Dyers and Colourists,

The American Association of Textile Chemists and Colorists," vol. 2, pages 2909-2922, and volume 3, pages 3341-3342 (1957). Preferred are the brightening agents having one or more amino groups in the molecule or other radical having basic characteristics. The particular fluorescent brightening agent employed will depend on the textile fabric being treated, in accordance with the recommendations in the Colour Index.

In the textile art, the brightening agents are generally classified as cotton, wool, and all-purpose brightening agents. Usually, with wool a stilbene group containing fluorescent agent is employed, but as above-indicated other fluorescent agents can be used. If the detergent composition is to be used to treat both wool and cottons, both a wool and a cotton or an all-purpose brightening agent can be employed.

There can be incorporated in a detergent composition comprising a condensation product and acidic material as defined hereinbefore, various filling agents, e.g., Glaubers salt, sodium chloride, potassium chloride, sodium hexametaphosphate, sodium pyrophosphate, monosodium phosphate, disodium phosphate and trisodium phosphate.

There can also be included suspending agents such as vlignin sulfonic acid and methyl cellulose, and bleaching M fabrics, improved flex abrasion resistance often is at an optimum at higher temperatures, e.g., from 85-100 C. However, increased cleansing power of a detergent, in-- creased brightening power of a fluorescent brightening agent and improved hand and texture can be noted at almost any temperature.

A usual procedure involves agitating the fabric in a solution of the composition at the desired temperature, usually at a liquor ratio of from to 50:1 for from about 5 minutes to one hour. A washing or scouring time of about 2030 minutes is ordinarily adequate, especially if very hot water is used. The fabric can then, if desired, be rinsed thoroughly and then dried.

The fabric can then be tested, if desired, for the enhanced properties described hereinbefore. Hand or handle is a subjective factor. A pleasing hand is one approaching the feel or handle of cashmere, in the case of woolens, and of long staple Egyptian cotton, in the case of cottons. In the examples hereinafter, the fabrics described were tested for tensile and tear strength and flex abrasion resistance by accepted tests on standard equipment.

In the examples below, all percentages are by weight.

Example I A 100 g. piece of dirty woven woolen cloth was washed in 2 liters of warm water containing 6 g. of a detergent composition having the following composition:

The fabric was rinsed thoroughly and dried. It was found to be cleaner, brighter and to have a better hand than another sample of the same fabric washed in a corresponding detergent composition in which the citric acid and condensation product was replaced by filler.

Similarly, 225 g. of the above composition will wash a 3.75 kg. load of mixed laundry in an agitator type automatic washing machine or the corresponding weight of delicate fabrics by hand to give a cleaner, brighter wash than the corresponding detergent without the citric acid and formaldehyde-arylsulfonic acid condensation product. Each, some, and all of the following changes in the above composition can be made while retaining the increased detergency, brightening and other desirable properties of the detergent composition:

(a) Part of the filler can be replaced by suspending agent,

e.g., 0.5% lignin sulfonic acid;

(b) The detergent can be varied from about 30% to about 43% with corresponding changes in the percentage of filler;

(c) The Uvitex W.G.S. can be replaced by Tinopal BVA or an equal proportion of each employed, or the fluorescent brightening agent eliminated;

(d) The sodium dodecylbenzenesulfonate can be replaced with sodium oleylsulfate, sodium laurylsulfate, sodium octadecylbenzenesulfonate, or replaced partially or completely with a nonionic detergent, e.g., Tergitol NPX alkaryl polyglycol;

(e) The Erional NW can be replaced by dinaphthylmethane disulfonic acid, dicresylmethane disulfonic acid, or other carbocyclic diarylalkane disulfonic acid;

(f) The citric acid can be varied from about to about 45%;

(g) The citric acid can be replaced by lactic acid;

(It) The citric acid can be replaced by tartaric acid;

(i) The formaldehyde-arylsulfonic acid condensation product can be varied from about 4% to about 25%, with corresponding changes in the proportion of filler.

6 Example II A g. sample of dirty woven woolen cloth was washed in 2 liters of 60 C. water containing 6 g. of a commercial detergent composition consisting of a wool fluorescent brightening agent, about 43% sodium dodecylbenzenesulfonate, and filler; 3.0 g. of citric acid, and 0.5 g. of Erional NW. The washed fabric was cleaner, brighter, and had a softer hand than an identical sample identically washed in water containing 6 g. of the commercial detergent only. It also had increased tensile strength compared with the cloth washed in commercial detergent only.

Example III Following the procedure of Example II, but boiling the cloth in the detergent compositions, the woolen cloth washed in the mixture containing citric acid and condensation product had greater flex abrasion resistance than the cloth washed in commercial detergent only and the starting unwashed cloth.

Example IV The following are detergent compositions intended primarily for mill use to clean and brighten woven and knitted woolen fabrics and yarn and to improve their hand, tensile strength and/or flex abrasion resistance.

A. Detergent:

A 100 g. sample of woven woolen greige fabric was washed at 70 C. for 20 minutes in 2 liters of water containing 8.15 g. of detergent composition A. It was then rinsed thoroughly and dried. The washed fabric was cleaner, brighter, and had greater flex abrasion resistance than the control sample washed only in the same amount of Tergitol NPX and sodium dodecylbenzenesulfonate as was present in composition A.

- A 100 g. sample of woven woolen greige fabric was washed at 60 C. for 30 minutes in 2 liters of water containing 4.9 g. of detergent composition B. The washed, rinsed and dried fabric was cleaner, brighter and had greater tensile strength and flex abrasion resistance than an identical sample washed only in the same amount of Tergitol NPX and sodium dodecylbenzenesulfonate as was present in composition B.

Similarly, another 100 g. sample of the same fabric was washed with detergent composition C at 60 C. for 30 minutes to produce a washed fabric that had markedly superior flex abrasion resistance, without loss of tensile strength, when compared with an identical sample washed with the same detergent, but without the citric acid and condensation product.

Example V The following is a detergent composition suitable for washing cotton fabrics as well as woven and knitted woolen fabrics.

Detergent:

Percent Sodium dodecylbenzenesulfonate 35 Citric acid 35 Soiled cotton fabrics washed in the above detergent composition display considerably greater brightness and appear cleaner than comparable fabrics washed in a comparable amount of a detergent composition in which the citric acid and condensation product have been omitted.

Each, some and all of the following changes in the above composition can be made while still retaining the enhanced properties thereof.

(a) The detergent can be varied between about 17% and about 45% with corresponding variations in the filler;

(b) The citric acid can be varied between about 10% and about 40% with corresponding variations in filler and/ or detergent;

(c) The condensation product can be varied between about and about 15% with corresponding variation in filler and/ or citric acid;

(d) The fluorescent brightening agent can be varied between about 2% and about 9%, with corresponding variations in filler;

(e) A nonionic detergent e.g., Tergitol NPX alkaryl polyglycol, can be substituted in the same or lesser proportions for the sodium dodecylbenzenesulfonate or added to the detergent composition with a corresponding reduction in filler;

(f) The sodium dodecylbenzenesulfonate can be replaced by sodium oleylsulfate.

Example VI A detergent composition corresponding exactly to that described in Example V, except that the formaldehydearylsulfonic acid condensation product was dinaphthyl- 2 methane disulfonic acid, was used in the same amount to wash dirty cotton fabric. The washed fabric was cleaner, brighter and had better strength than samples of the same fabric washed in a comparable amount of detergent in which the citric acid and condensation product was eliminated.

What is claimed is:

1. A detergent composition consisting essentially of (1).

from 14.5% to 45% of a detergent selected from the group consisting of synthetic organic non-soap anionic and nonionic detergents, (2) from 4 to 25% of a compound selected from the group consisting of a water soluble condensation product of formaldehyde and a carbocyclic aryl sulfonic acid, and a water soluble salt thereof, and (3) an amount, from 10% to 45%, of a hydroxy organic acid selected from the group consisting of citric acid, lactic acid and tartaric acid sufiicient to render a 0.5 aqueous solution of the detergent composition initially acidic at a pH of between about 2 and about 5, the proportion of (2) to (3) being from 1:100 to 6:1.

2. The detergent composition of claim 1 wherein the hydroxy organic acid is citric acid.

3. The detergent composition of claim 1 wherein the condensation product is the water soluble condensation product of formaldehyde and naphthalene sulfonic acid.

4. The detergent composition of claim 1 containing from 2% to 9% of a fluorescent brightening agent.

5. A detergent composition consisting essentially of ((1) from 17% to 45% of sodium dodecylbenzene sulfonate, (2) from 5% to 15% of the water soluble condensation product of formaldehyde and a carbocyclic aryl sulfonic acid and (3) an amount, from 10% to 40%, of citric acid suflicient to render a 0.5% aqueous solution of the detergent composition initially acidic at a pH of between about 2 and about 5, and (4) from 2% to 9% of a fluorescent brightening agent, the ratio of (2) to (3) being from 1:100 to 6:1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF (1) FROM 14.5% TO 45% OF A DETERGENT SELECTED FROM THE GROUP CONSISTING OF SYNTHETIC ORGANIC NON-SOAP ANIONIC AND NONIONIC DETERGENTS, (2) FROM 4 TO 25% OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF A WATER DSOLUBLE CONDENSATION PRODUCT OF FORMALDEHYDE AND A CARBOCYLIC ARYL SULFONIC ACID, AND A WATER SOLUBLE SALT THEREOF, AND (3) AN AMOUNT, FROM 10% TO 45%, OF A HYDROXY ORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF CITRIC ACID, LACTIC ACID AND TARTARIC ACID SUFFICIENT TO RENDER A 0.5% AQUEOUS SOLUTION OF THE DETERGENT COMPOSITION INITIALLY ACIDIC AT A PH OF BETWEEN ABOUT 2 AND ABOUT, 5 THE PROPORTION OF (2) TO (3) BEING FROM 1:100 TO 6:1. 